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Peer-reviewedCC BY 4.0JACS Au

Selective Electrochemical E –Semihydrogenation of Alkyl Alkynes with Main Metal Electrodes and Water

  • Miquel Molina−García1
  • Susi Hervàs−Arnandís1
  • Jordi Aragón2
  • Marta Mon1
  • Antonio Leyva−Pérez1
  1. 1Consejo Superior de Investigaciones Científicas−Universitat Politècnica de València , , Avda. de Los Naranjos s/n , ,
  2. 2SEDQ Healthy Crops SL. , Carrer de Llull 41 , ,
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Abstract

The semihydrogenation reaction of alkynes to E-alkenes is still a challenge in modern and sustainable organic chemistry, particularly for alkyl alkynes where allyl H-abstraction, alkynyl hydrofunctionalization, and overhydrogenation by reactions easily occur. Here we show that a selective E–electrosemihydrogenation reaction of alkyl alkynes proceeds with Mg and Al as sacrificial electrodes in THF/water mixtures. The reaction is extendable to aromatic alkynes and deuteration processes, proceeds with >98% Faradaic efficiency (FA) in an undivided cell, avoids the hydrogen evolution reaction (HER), and achieves E/Z ratios >3:1, three times higher than any recent electro(catalytic) method reported as far as we know. Mechanistic studies based on reactive, kinetic, isotopic, and computational experiments, among others, reveal that the success of this transition-metal-free electrochemical semihydrogenation reaction relies on the direct one-electron cathodic reduction of the alkyne, circumventing the typical H activation triggered by transition metals and enabling the rapid isomerization of the so-formed vinyl anion radical to the more stable E isomer after final protonation. These results open the way to directly obtain E-alkyl alkenes from the corresponding alkynes with just highly abundant metals, water, and electricity, with broad application in industrial chemistry, herein demonstrated for the gram-scale synthesis of a pheromone precursor.

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Cite

BibTeXRIS
BibTeX
@article{molinagarcia2026selective,
  title = {{Selective Electrochemical E –Semihydrogenation of Alkyl Alkynes with Main Metal Electrodes and Water}},
  author = {Miquel Molina−García and Susi Hervàs−Arnandís and Jordi Aragón and Marta Mon and Antonio Leyva−Pérez},
  journal = {JACS Au},
  year = {2026},
  month = oct,
  doi = {10.1021/jacsau.6c01179},
  url = {https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01179/5459565/Selective-Electrochemical-E-Semihydrogenation-of},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Selective Electrochemical E –Semihydrogenation of Alkyl Alkynes with Main Metal Electrodes and Water
AU  - Miquel Molina−García
AU  - Susi Hervàs−Arnandís
AU  - Jordi Aragón
AU  - Marta Mon
AU  - Antonio Leyva−Pérez
PY  - 2026
DA  - 2026/10/28
JO  - JACS Au
DO  - 10.1021/jacsau.6c01179
UR  - https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01179/5459565/Selective-Electrochemical-E-Semihydrogenation-of
AB  - The semihydrogenation reaction of alkynes to E-alkenes is still a challenge in modern and sustainable organic chemistry, particularly for alkyl alkynes where allyl H-abstraction, alkynyl hydrofunctionalization, and overhydrogenation by reactions easily occur. Here we show that a selective E–electrosemihydrogenation reaction of alkyl alkynes proceeds with Mg and Al as sacrificial electrodes in THF/water mixtures. The reaction is extendable to aromatic alkynes and deuteration processes, proceeds with >98% Faradaic efficiency (FA) in an undivided cell, avoids the hydrogen evolution reaction (HER), and achieves E/Z ratios >3:1, three times higher than any recent electro(catalytic) method reported as far as we know. Mechanistic studies based on reactive, kinetic, isotopic, and computational experiments, among others, reveal that the success of this transition-metal-free electrochemical semihydrogenation reaction relies on the direct one-electron cathodic reduction of the alkyne, circumventing the typical H activation triggered by transition metals and enabling the rapid isomerization of the so-formed vinyl anion radical to the more stable E isomer after final protonation. These results open the way to directly obtain E-alkyl alkenes from the corresponding alkynes with just highly abundant metals, water, and electricity, with broad application in industrial chemistry, herein demonstrated for the gram-scale synthesis of a pheromone precursor.
SN  - 2691-3704
ER  -